Substituted 6-(2-methoxyphenyl) triazolopyrimides as fungicides

ABSTRACT

Substituted 6-(2-methoxy-phenyl)-triazolopyrimidines of formula I                  
 
in which
         R 1  and R 2  independently denote hydrogen or alkyl, alkenyl, alkynyl, or alkadienyl, haloalkyl, haloalkenyl, cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or
           where R 1  and R 2  radicals may be unsubstituted or substituted as defined in the description, or   
           R 1  and R 2  together with the interjacent nitrogen atom represent a 5- or 6-membered heterocyclic ring, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which may be substituted;   L 1 , L 2  independently denote hydrogen or halogen, provided that at least one from L 1  or L 2  is halogen;   X is halogen, cyano, alkyl, alkoxy, haloalkoxy or alkenyloxy;       

     processes for their preparation, compositions containing them and to their use for combating phytopathogenic fungi.

The invention relates to substituted6-(2-methoxy-phenyl)-triazolopyrimidines of formula I

in which

-   -   R¹ and R² independently denote hydrogen or C₁–C₁₀-alkyl,        C₂–C₁₀-alkenyl, C₂–C₁₀-alkynyl, or C₄–C₁₀-alkadienyl,        C₁–C₁₀-haloalkyl, C₂–C₁₀-haloalkenyl, C₃–C₁₀-cycloalkyl, phenyl,        naphthyl, or        -   5- or 6-membered heterocyclyl, containing one to four            nitrogen atoms or one to three nitrogen atoms and one sulfur            or oxygen atom, or 5- or 6-membered heteroaryl, containing            one to four nitrogen atoms or one to three nitrogen atoms            and one sulfur or oxygen atom, or        -   where R¹ and R² radicals may be unsubstituted or partly or            fully halogenated or may carry one to three groups R^(a),        -   R^(a) is cyano, nitro, hydroxyl, C₁–C₆-alkyl,            C₃–C₆-cycloalkyl, C₁–C₆-alkoxy, C₁–C₆-alkylthio,            C₁–C₆-alkylamino, di-C₁–C₆-alkylamino, C₂–C₆-alkenyl,            C₂–C₆-alkenyloxy, C₂–C₆-alkynyl, C₃–C₆-alkynyloxy and            C₁–C₄-alkylenedioxy; or    -   R¹ and R² together with the interjacent nitrogen atom represent        a 5- or 6-membered heterocyclic ring, containing one to four        nitrogen atoms or one to three nitrogen atoms and one sulfur or        oxygen atom, which may be substituted by one to three R^(a)        radicals;    -   L¹, L² independently denote hydrogen or halogen, provided that        at least one from L¹ or L² is halogen;    -   X is halogen, cyano, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy        or C₃–C₈-alkenyloxy.

Moreover, the invention relates to processes for their preparation,compositions containing them and to their use for combatingphytopathogenic fungi.

6-Phenyl-7-amino-triazolopyrimidines are generally known from U.S. Pat.No. 4,567,262.

Triazolopyrimidines with a trifluorophenyl group in 6-position aredisclosed in WO-A 98/46607 and EP-A 945 453.

From WO-A 98/46608 diverse 6-phenyl-triazolopyrimidines are known, whichare substituted in the 7-position by fluorinated alkylamines.

From EP-A 550 113 triazolopyrimidines with a 2-methoxy substituted6-phenyl group are known.

The compounds disclosed in the documents discussed above are said to beactive against various phytopathogenic fungi.

It is an object of the present invention to provide compounds havingimproved fungicidal activity.

We have found that this object is achieved by the compounds defined atthe outset. Furthermore, we have found processes for their preparation,compositions comprising them and methods for controlling phytopathogenicfungi using the compounds I.

The compounds of formula I differ from the compounds known from closestprior art EP-A 550 113 in the 2-methoxy-phenyl group, which is furtherhalogenated.

Compounds of formula I can be prepared similar to the conditions knownfrom EP-A 550 113. Preferably the preparation of compounds of formula Ias defined above comprises reacting 5-amino-triazole with2-(2-methoxy-phenyl)-substituted malonic acid ester of formula II, inwhich

R represents alkyl, preferably C₁–C₆-alkyl, in particular methyl orethyl, under alkaline conditions, preferably using high boiling tertiaryamines as for example tri-n-butylamine as disclosed for example by EP-A770 615 to yield compounds of formula III.

The resulting 5,7-dihydroxy-6-phenyl-triazolopyrimidine of formula III,wherein L¹ and L² are as defined for formula I, is subsequently treatedwith a halogenating agent, preferably with a brominating or chlorinatingagent, such as phosphorus oxybromide or phosphorus oxychloride, neat orin the presence of a solvent to give IV.

The reaction is suitably carried out at a temperature in the range from0° C. to 150° C., the preferred reaction temperature being from 80° C.to 125° C. as disclosed for example by EP-A 770 615.

Dihalotriazolopyrimidine IV is further reacted with an amine of formulaV

in which R¹ and R² are as defined in formula I to produce compounds offormula I in which X is halogen.

The reaction between the 5,7-dihalo compound IV and the amine of formulaV can be carried out under conditions known from WO-A 98/46608. Thereaction is preferably carried out in the presence of a solvent.Suitable solvents include ethers, such as dioxane, diethyl ether and,especially, tetrahydrofuran, halogenated hydrocarbons such asdichloromethane and aromatic hydrocarbons, for example toluene.

The reaction is suitably carried out at a temperature in the range from0° C. to 70° C., the preferred reaction temperature being from 10° C. to35° C.

It is also preferred that the reaction is carried out in the presence ofa base. Suitable bases include tertiary amines, such as triethylamine,and inorganic bases, such as potassium carbonate or sodium carbonate.Alternatively, an excess of the compound of formula V may serve as abase.

Compounds of formula I in which X denotes cyano, C₁–C₆-alkoxy,C₁–C₆-haloalkoxy or C₃–C₈-alkenyloxy can be prepared by reactingcompounds I in which X is halogen, preferably chloro, with compounds offormula VI, which are, dependent from the value of X′ to be introducedto yield formula I compounds, an an organic cyano salt, an alkoxylate,haloalkoxylate or an alkenyloxylate, respectively, preferably in thepresence of a a solvent. The cation M in formula VI has minor influence;for practical and economical reasons usually ammonium-,tetraalkylammonium- or alkalimetal- and earth metal salts are preferred.

The reaction is suitably carried out at a temperature in the range from0 to 120° C., the preferred reaction temperature being from 10 to 40° C.[cf. J. Heterocycl. Chem. Vol.12, p. 861–863 (1975)].

Suitable solvents include ethers, such as dioxane, diethyl ether and,especially, tetrahydrofuran, halogenated hydrocarbons such asdichloromethane and aromatic hydrocarbons, for example toluene.

Compounds of formula I in which X denotes C₁–C₆-alkyl can be prepared byreacting compounds I in which X is halogen, preferably chloro, withmalonic acid esters of formula VII, wherein X″ denotes H or C₁–C₅-alkyland R denotes C₁–C₄-alkyl, to compounds of formula VIII anddecarboxylation under conditions described in U.S. Pat. No. 5,994,360.

Accordingly, the invention relates to the novel intermediates offormulae II, III and IV.

The compounds of formula II are preferably prepared by reaction of thecorresponding substituted bromobenzenes with sodium dial-kylmalonates inthe presence of a copper(I) salt [cf. Chemistry Letters, pp. 367–370,1981; EP-A 10 02 788].

The compounds of formula II may also be prepared by reaction of an alkyl2-(2-methoxy-phenyl)-acetate with dialkylcarbonate in the presence of astrong base, preferably sodium ethoxide and sodium hydride (cf.Heterocycles, pp. 1031–1047, 1996).

The substituted phenylacetates which are the starting compounds forcompounds of formula II are known and commercially available, and/orthey are obtainable by generally known methods.

The reaction mixtures are worked up in a customary manner, for exampleby mixing with water, phase separation and, if required, chromatographicpurification of the crude products. Some of the end products areobtained in the form of colorless or slightly brownish, viscous oils,which are purified or freed from volatile components under reducedpressure and at moderately elevated temperatures. If the end productsare obtained as solids, purification can also be carried out byrecrystallization or digestion.

If individual compounds I are not obtainable by the routes describedabove, they can be prepared by derivatization of other compounds I.

In the symbol definitions given in the formulae above, collective termswere used which generally represent the following substituents:

-   -   halogen: fluorine, chlorine, bromine and iodine;    -   C₁–C₁₀-alkyl: saturated, straight-chain or branched hydrocarbon        radicals having 1 to 10, especially 1 to 6 carbon atoms, for        example C₁–C₄-alkyl as mentioned above or pentyl, 1-methylbutyl,        2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl,        1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,        1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,        1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,        2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,        1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,        1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and        1-ethyl-2-methylpropyl;    -   C₂–C₁₀-alkenyl: unsaturated, straight-chain or branched        hydrocarbon radicals having 2 to 10, especially 2 to 6 carbon        atoms and a double bond in any position, for example ethenyl,        1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,        3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,        1-methyl-2-propenyl and 2-methyl-2-propenyl; C₂–C₁₀-alkynyl:        straight-chain or branched hydrocarbon radicals having 2 to 10,        especially 2 to 4 carbon atoms and a triple bond in any        position, for example ethynyl, 1-propynyl, 2-propynyl,        1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2-propynyl;    -   C₁–C₁₀-haloalkyl and haloalkyl moieties of C₁–C₆-haloalkoxy:        straight-chain or branched alkyl groups having 1 to 6 or 10,        preferably 1 to 4 carbon atoms (as mentioned above), where the        hydrogen atoms in these groups may be partially or fully        replaced by halogen atoms as mentioned above, for example        C₁–C₂-haloalkoxy, such as chloromethoxy, bromomethoxy,        dichloromethoxy, trichloromethoxy, fluoromethoxy,        difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy,        dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy,        1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy,        2,2-difluoroethoxy, 2,2,2-trifluoroethoxy,        2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy,        2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and        pentafluoroethoxy;    -   C₃–C₁₀-cycloalkyl: mono- or bicyclic cycloalkyl groups having 3        to 10 carbon atoms; monocyclic groups preferably have 3 to 8,        especially 3 to 6 ring members, bicyclic groups preferably have        8 to 10 ring members.

A 5- or 6-membered heterocyclyl group, containing one to four nitrogenatoms or one to three nitrogen atoms and one sulfur or oxygen atom,preferably one oxygen atom, for example 1-pyrimidinyl, 2-pyrimidinyl,morpholin-4-yl.

5-membered heteroaryl, containing one to four nitrogen atoms or one tothree nitrogen atoms and one sulfur or oxygen atom: 5-memberedheteroaryl groups which, in addition to carbon atoms, may contain one tofour nitrogen atoms or one to three nitrogen atoms and one sulfur oroxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl,3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl,5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl,3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl,5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl,4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl,1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl;

6-membered heteroaryl, containing one to four nitrogen atoms: 6-memberedheteroaryl groups which, in addition to carbon atoms, may contain one tothree or one to four nitrogen atoms as ring members, for example2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.

With respect to their intended use, preference is given totriazolopyrimidines of the formula I having the following substituents,where the preference is valid in each case on its own or in combination:

A preferred cycloalkyl moiety is cyclopentyl being optionallysubstituted by one or more nitro, cyano, C₁–C₆-alkyl, C₁–C₆-alkoxygroups.

A preferred heteroaryl moiety is pyridyl, pyrimidyl, pyrazolyl orthienyl.

Preference is given to compounds of formula I in which any alkyl orhaloalkyl part of the groups R¹ or R², which may be straight chained orbranched, contains up to 10 carbon atoms, preferably 1 to 9 carbonatoms, more preferably 2 to 6 carbon atoms, any alkenyl or alkynyl partof the substituents R¹ or R² contains up to 10 carbon atoms, preferably2 to 9 carbon atoms, more preferably 3 to 6 carbon atoms, any cycloalkylpart of the substituents R¹ or R² contains from 3 to 10 carbon atoms,preferably from 3 to 8 carbon atoms, more preferably from 3 to 6 carbonatoms, and any bicycloalkyl part of the substituents R¹ or R² containsfrom 5 to 9 carbon atoms, preferably from 7 to 9 carbon atoms. Anyalkyl, alkenyl or alkynyl group may be linear or branched.

Likewise, preference is given to compounds of formula I wherein R¹ isnot hydrogen.

Compounds of formula I are preferred in which R¹ represents astraight-chained or branched C₁–C₁₀-alkyl, in particular a branchedC₃–C₁₀-alkyl group, a C₃–C₈-cycloalkyl, a C₅–C₉-bicycloalkyl, aC₃–C₈-cycloalkyl-C₁–C₆-alkyl, C₁–C₁₀-alkoxy-C₁–C₆-alkyl, aC₁–C₁₀-haloalkyl or a phenyl group being optionally substituted by oneto three halogen atoms or C₁–C₁₀-alkyl or C₁–C₁₀-alkoxy groups.

Particular preference is given to compounds I in which R² representshydrogen, C₁–C₁₀-alkyl or C₁–C₁₀-haloalkyl, in particular hydrogen.

Besides, particular preference is given to compounds I in which R² ishydrogen.

Moreover, particular preference is given to compounds I in which R² ismethyl.

Furthermore, particular preference is given to compounds I in which R²is ethyl.

If R¹ denotes C₁–C₁₀-haloalkyl, preferably polyfluorinated alkyl, inparticular 2,2,2-trifluoroethyl, 2-(1,1,1-trifluoropropyl) or2-(1,1,1-trifluorobutyl), R² preferably represents hydrogen.

If R¹ denotes optionally substituted C₃–C₈-cycloalkyl, preferablycyclopentyl or cyclohexyl, R² preferably represents hydrogen orC₁–C₆-alkyl.

Moreover, particular preference is given to compounds I in which R¹ andR² together with the interjacent nitrogen atom form an optionallysubstituted heterocyclic ring, preferably an optionally substitutedC₃–C₇-heterocyclic ring, in particular pyrrolidine, piperidine,tetrahydropyridine, in particular 1,2,3,6-tetrahydropyridine or azepanewhich is optionally substituted by one or more C₁–C₁₀-alkyl groups.

Preference is given to compounds of formula I in which any alkyl part ofthe groups R¹ or R², which may be straight chained or branched, contains1 to 9 carbon atoms, more preferably 2 to 6 carbon atoms, any alkenyl oralkynyl part of the substituents R¹ or R² contains 2 to 9 carbon atoms,more preferably 3 to 6 carbon atoms, any cycloalkyl part of thesubstituents R¹ or R² contains from 3 to 10 carbon atoms, preferablyfrom 3 to 8 carbon atoms, more preferably from 3 to 6 carbon atoms, andany bicycloalkyl part of the substituents R¹ or R² contains from 7 to 9carbon atoms. Any alkyl, alkenyl or alkynyl moiety may be linear orbranched.

Compounds of formula I are preferred in which R¹ represents astraight-chained or branched C₁–C₁₀-alkyl, in particular branchedC₃–C₁₀-alkyl, a C₃–C₈-cycloalkyl, C₅–C₉-bicycloalkyl,C₃–C₈-cycloalkyl-C₁–C₆-alkyl, C₁–C₁₀-alkoxy-C₁–C₆-alkyl, or phenyl beingoptionally substituted by one to three C₁–C₁₀-alkyl or C₁–C₁₀-alkoxygroups.

Compounds of formula I are preferred wherein not R¹ and R² both arehydrogen.

Particular preference is given to compounds I in which R² representshydrogen or C₁–C₁₀-alkyl, in particular hydrogen.

Moreover, particular preference is given to compounds I in which R² ismethyl or ethyl.

If R¹ denotes an optionally substituted C₃–C₈-cycloalkyl group,preferably cyclopentyl or cyclohexyl, R² preferably represents hydrogenor C₁–C₆-alkyl.

Moreover, particular preference is given to compounds I in which R¹ andR² together with the interjacent nitrogen atom form an optionallysubstituted heterocyclic ring, preferably an optionally substitutedC₃–C₇-heterocyclic ring, in particular a pyrrolidine, piperidine,tetrahydropyridine, in particular 1,2,3,6-tetrahydropyridine or azepanering which is optionally substituted by one or more C₁–C₁₀-alkyl groups.

Likewise, particular preference is given to compounds I in which R² ishydrogen.

Furthermore, preference is given to compounds I in which L¹ is fluoro orchloro, particularly fluoro.

Besides, particular preference is given to compounds I in which L² ishydrogen, chloro or fluoro, particularly fluoro.

Likewise, particular preference is given to compounds I in which L¹ isfluoro and L² is hydrogen.

Particular preference is also given to compounds I in which L¹ and L²both are fluoro.

Moreover, particular preference is also given to compounds I in which L¹and/or L² is methyl.

Besides, particular preference.is given to compounds I in which X ischloro or bromo, especially chloro.

Moreover, preference is given to compounds I in which X is cyano ormethyl.

Furthermore, particular preference is given to compounds I in which X ismethoxy, ethoxy, n-propoxy, iso-propoxy, allyloxy, or 3-methylallyloxy.

The particularly preferred embodiments of the intermediates with respectto the variables correspond to those of the radicals X, R¹, R², L¹ andL² of formula I.

Included in the scope of the present invention are (R) and (S) isomersof compounds of general formula I having a chiral center and theracemates thereof, and salts, N-oxides and acid addition compounds.

With respect to their use, particular preference is given to thecompounds I compiled in the tables below. The groups mentioned in thetables for a substituent are furthermore for their part, independentlyof the combination in which they are mentioned, a particularly preferredembodiment of the respective substituents.

Table 1

Compounds of the formula I, in which X is chloro, L¹ is hydrogen, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 2

Compounds of the formula I, in which X is chloro, L¹ is hydrogen, L² ischloro and R¹ and R² correspond to one row in Table A

Table 3

Compounds of the formula I, in which X is chloro, L¹ is fluoro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 4

Compounds of the formula I, in which X is chloro, L¹ is fluoro, L² ischloro and R¹ and R² correspond to one row in Table A

Table 5

Compounds of the formula I, in which X is chloro, L¹ and L² are fluoroand R¹ and R² correspond to one row in Table A

Table 6

Compounds of the formula I, in which X is chloro, L¹ is chloro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 7

Compounds of the formula I, in which X is chloro, L¹ and L² are chloroand R¹ and R² correspond to one row in Table A

Table 8

Compounds of the formula I, in which X is chloro, L¹ is chloro, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 9

Compounds of the formula I, in which X is bromo, L¹ is hydrogen, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 10

Compounds of the formula I, in which X is bromo, L¹ is hydrogen, L² ischloro and R¹ and R² correspond to one row in Table A

Table 11

Compounds of the formula I, in which X is bromo, L¹ is fluoro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 12

Compounds of the formula I, in which X is bromo, L¹ is fluoro, L² ischloro and R¹ and R² correspond to one row in Table A

Table 13

Compounds of the formula I, in which X is bromo, L¹ and L² are fluoroand R¹ and R² correspond to one row in Table A

Table 14

Compounds of the formula I, in which X is bromo, L¹ is chloro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 15

Compounds of the formula I, in which X is bromo, L¹ and L² are chloroand R¹ and R² correspond to one row in Table A

Table 16

Compounds of the formula I, in which X is bromo, L¹ is chloro, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 17

Compounds of the formula I, in which X is cyano, L¹ is hydrogen, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 18

Compounds of the formula I, in which X is cyano, L¹ is hydrogen, L² ischloro and R¹ and R² correspond to one row in Table A

Table 19

Compounds of the formula I, in which X is cyano, L¹ is fluoro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 20

Compounds of the formula I, in which X is cyano, L¹ is fluoro, L² ischloro and R¹ and R² correspond to one row in Table A

Table 21

Compounds of the formula I, in which X is cyano, L¹ and L² are fluoroand R¹ and R² correspond to one row in Table A

Table 22

Compounds of the formula I, in which X is cyano, L¹ is chloro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 23

Compounds of the formula I, in which X is cyano, L¹ and L² are chloroand R¹ and R² correspond to one row in Table A

Table 24

Compounds of the formula I, in which X is cyano, L¹ is chloro, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 25

Compounds of the formula I, in which X is methoxy, L¹ is hydrogen, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 26

Compounds of the formula I, in which X is methoxy, L¹ is hydrogen, L² ischloro and R¹ and R² correspond to one row in Table A

Table 27

Compounds of the formula I, in which X is methoxy, L¹ is fluoro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 28

Compounds of the formula I, in which X is methoxy, L¹ is fluoro, L² ischloro and R¹ and R² correspond to one row in Table A

Table 29

Compounds of the formula I, in which X is methoxy, L¹ and L² are fluoroand R¹ and R² correspond to one row in Table A

Table 30

Compounds of the formula I, in which X is methoxy, L¹ is chloro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 31

Compounds of the formula I, in which X is methoxy, L¹ and L² are chloroand R¹ and R² correspond to one row in Table A

Table 32

Compounds of the formula I, in which X is methoxy, L¹ is chloro, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 33

Compounds of the formula I, in which X is methyl, L¹ is hydrogen, L² isfluoro and R¹ and R² correspond to one row in Table A

Table 34

Compounds of the formula I, in which X is methyl, L¹ is hydrogen, L² ischloro and R¹ and R² correspond to one row in Table A

Table 35

Compounds of the formula I, in which X is methyl, L¹ is fluoro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 36

Compounds of the formula I, in which X is methyl, L¹ is fluoro, L² ischloro and R¹ and R² correspond to one row in Table A

Table 37

Compounds of the formula I, in which X is methyl, L¹ and L² are fluoroand R¹ and R² correspond to one row in Table A

Table 38

Compounds of the formula I, in which X is methyl, L¹ is chloro, L² ishydrogen and R¹ and R² correspond to one row in Table A

Table 39

Compounds of the formula I, in which X is methyl, L¹ and L² are chloroand R¹ and R² correspond to one row in Table A

Table 40

Compounds of the formula I, in which X is methyl, L¹ is chloro, L² isfluoro and R¹ and R² correspond to one row in Table A

TABLE A I

No. R¹ R² A-1 H H A-2 CH₂CH₃ H A-3 CH₂CH₃ CH₃ A-4 CH₂CH₃ CH₂CH₃ A-5CH₂CF₃ H A-6 CH₂CF₃ CH₃ A-7 CH₂CF₃ CH₂CH₃ A-8 CH₂CCl₃ H A-9 CH₂CCl₃ CH₃A-10 CH₂CCl₃ CH₂CH₃ A-11 CH₂CH₂CH₃ H A-12 CH₂CH₂CH₃ CH₃ A-13 CH₂CH₂CH₃CH₂CH₃ A-14 CH₂CH₂CH₃ CH₂CH₂CH₃ A-15 CH(CH₃)₂ H A-16 CH(CH₃)₂ CH₃ A-17CH(CH₃)₂ CH₂CH₃ A-18 (±) CH(CH₃)—CH₂CH₃ H A-19 (±) CH(CH₃)—CH₂CH₃ CH₃A-20 (±) CH(CH₃)—CH₂CH₃ CH₂CH₃ A-21 (S) CH(CH₃)—CH₂CH₃ H A-22 (S)CH(CH₃)—CH₂CH₃ CH₃ A-23 (S) CH(CH₃)—CH₂CH₃ CH₂CH₃ A-24 (R)CH(CH₃)—CH₂CH₃ H A-25 (R) CH(CH₃)—CH₂CH₃ CH₃ A-26 (R) CH(CH₃)—CH₂CH₃CH₂CH₃ A-27 (±) CH(CH₃)—CH(CH₃)₂ H A-28 (±) CH(CH₃)—CH(CH₃)₂ CH₃ A-29(±) CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-30 (S) CH(CH₃)—CH(CH₃)₂ H A-31 (S)CH(CH₃)—CH(CH₃)₂ CH₃ A-32 (S) CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-33 (R)CH(CH₃)—CH(CH₃)₂ H A-34 (R) CH(CH₃)—CH(CH₃)₂ CH₃ A-35 (R)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-36 (±) CH(CH₃)—C(CH₃)₃ H A-37 (±)CH(CH₃)—C(CH₃)₃ CH₃ A-38 (±) CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-39 (S)CH(CH₃)—C(CH₃)₃ H A-40 (S) CH(CH₃)—C(CH₃)₃ CH₃ A-41 (S) CH(CH₃)—C(CH₃)₃CH₂CH₃ A-42 (R) CH(CH₃)—C(CH₃)₃ H A-43 (R) CH(CH₃)—C(CH₃)₃ CH₃ A-44 (R)CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-45 (±) CH(CH₃)—CF₃ H A-46 (±) CH(CH₃)—CF₃ CH₃A-47 (±) CH(CH₃)—CF₃ CH₂CH₃ A-48 (S) CH(CH₃)—CF₃ H A-49 (S) CH(CH₃)—CF₃CH₃ A-50 (S) CH(CH₃)—CF₃ CH₂CH₃ A-51 (R) CH(CH₃)—CF₃ H A-52 (R)CH(CH₃)—CF₃ CH₃ A-53 (R) CH(CH₃)—CF₃ CH₂CH₃ A-54 (±) CH(CH₃)—CCl₃ H A-55(±) CH(CH₃)—CCl₃ CH₃ A-56 (±) CH(CH₃)—CCl₃ CH₂CH₃ A-57 (S) CH(CH₃)—CCl₃H A-58 (S) CH(CH₃)—CCl₃ CH₃ A-59 (S) CH(CH₃)—CCl₃ CH₂CH₃ A-60 (R)CH(CH₃)—CCl₃ H A-61 (R) CH(CH₃)—CCl₃ CH₃ A-62 (R) CH(CH₃)—CCl₃ CH₂CH₃A-63 CH₂C(CH₃)═CH₂ H A-64 CH₂C(CH₃)═CH₂ CH₃ A-65 CH₂C(CH₃)═CH₂ CH₂CH₃A-66 cyclopentyl H A-67 cyclopentyl CH₃ A-68 cyclopentyl CH₂CH₃ A-69—(CH₂)₂CH(CH₃)(CH₂)₂—

The compounds I are suitable as fungicides. They have outstandingactivity against a broad spectrum of phytopathogenic fungi, inparticular from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some of them act systemically, and theycan be employed in crop protection as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ona variety of crop plants such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruitspecies, ornamentals and vegetables such as cucumbers, beans, tomatoes,potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

-   -   Alternaria species, Podosphaera species, Sclerotinia species,        Physalospora canker on vegetables and fruit,    -   Botrytis cinerea (gray mold) an strawberries, vegetables,        ornamentals and grapevines,    -   Corynespora cassiicola on cucumbers,    -   Colletotrichum species on fruit and vegetables,    -   Diplocarpon rosae on roses,    -   Elsinoe fawcetti and Diaporthe citri on citrus fruit,    -   Sphaerotheca species on cucurbits, strawberries and roses,    -   Cercospora species on peanuts, sugar beets and aubergines,    -   Erysiphe cichoracearum on cucurbits,    -   Leveillula taurica on paprika, tomatoes and aubergines,    -   Mycosphaerella species on apples and japanese apricot,    -   Phyllactinia kakicola, Gloesporium kaki on japanese apricot,    -   Gymnosporangium yamadae, Leptothyrium pomi, Podosphaera        leucotricha and Gloedes pomigena on apples,    -   Cladosporium carpophilum on pears and japanese apricot,    -   Phomopsis species on pears,    -   Phytophthora species on citrus fruit, potatoes, onions,        especially Phytophthora infestans on potatoes and tomatoes,    -   Blumeria graminis (powdery mildew) on cereals,    -   Fusarium- and Verticillium species on various plants,    -   Glomerella cingulata on tee,    -   Drechslera- and Bipolaris species on cereals and rice,    -   Mycosphaerella species on bananas and peanuts,    -   Plasmopara viticola on grapevines,    -   Personospora species on onions, spinach and chrysantemum,    -   Phaeoisariopsis vitis and Sphaceloma ampelina on grapefruits,    -   Pseudocercosporella herpotrichoides on wheat and barley,    -   Pseudoperonospora species on hop and cucumbers,    -   Puccinia species and Typhula species on cereals and turf,    -   Pyricularia oryzae on rice,    -   Rhizoctonia species on cotton, rice and turf,    -   Stagonospora nodorum and Septoria tritici on wheat,    -   Uncinula necator on grapevines,    -   Ustilago species on cereals and sugar cane, and    -   Venturia species (scab) on apples and pears.

Moreover, the compounds I are suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (e.g. wood,paper, paint dispersions, fibers and tissues) and in the protection ofstored products.

The compounds I are applied by treating the fungi, or the plants, seeds,materials or the soil to be protected against fungal infection, with afungicidally active amount of the active ingredients. Application can beeffected both before and after infection of the materials, plants orseeds by the fungi.

In general, the fungicidal compositions comprise from 0.1 to 95,preferably 0.5 to 90, % by weight of active ingredient.

When used in crop protection, the rates of application are from 0.01 to2.0 kg of active ingredient per ha, depending on the nature of theeffect desired.

In the treatment of seed, amounts of active ingredient of from 0.001 to0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram ofseed.

When used in the protection of materials or stored products, the rate ofapplication of active ingredient depends on the nature of the field ofapplication and on the effect desired. Rates of applicationconventionally used in the protection of materials are, for example,from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredientper cubic meter of material treated.

The compounds I can be converted into the customary formulations, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the particular purpose; in any case, it shouldguarantee a fine and uniform distribution of the compound according tothe invention.

The formulations are prepared in a known manner, e.g. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolvents as auxiliary solvents if water is used as the diluent.Auxiliaries which are suitable are essentially: solvents such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol,butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.highly-disperse silica, silicates); emulsifiers such as non-ionic andanionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylaryl-sulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof napthalenesulfonic acid with phenol or formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanone, cyclohexanone, chlorobenzene, isophorone,strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water.

Powders, materials for scattering and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Examples of solid carriers are mineral earths, such assilicas, silica gels, silicates, talc, kaolin, attaclay, limestone,lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calciumsulfate, magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders and othersolid carriers.

In general, the formulations comprise of from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active ingredient. Theactive ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are exemplary formulations:

-   -   I. 5 parts by weight of a compound according to the invention        are mixed intimately with 95 parts by weight of finely divided        kaolin. This gives a dust which comprises 5% by weight of the        active ingredient.    -   II. 30 parts by weight of a compound according to the invention        are mixed intimately with a mixture of 92 parts by weight of        pulverulent silica gel and 8 parts by weight of paraffin oil        which had been sprayed onto the surface of this silica gel. This        gives a formulation of the active ingredient with good adhesion        properties (comprises 23% by weight of active ingredient).    -   III. 10 parts by weight of a compound according to the invention        are dissolved in a mixture composed of 90 parts by weight of        xylene, 6 parts by weight of the adduct of 8 to 10 mol of        ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2        parts by weight of calcium dodecylbenzenesulfonate and 2 parts        by weight of the adduct of 40 mol of ethylene oxide and 1 mol of        castor oil (comprises 9% by weight of active ingredient).    -   IV. 20 parts by weight of a compound according to the invention        are dissolved in a mixture composed of 60 parts by weight of        cyclohexanone, 30 parts by weight of isobutanol, 5 parts by        weight of the adduct of 7 mol of ethylene oxide and 1 mol of        isooctylphenol and 5 parts by weight of the adduct of 40 mol of        ethylene oxide and 1 mol of castor oil (comprises 16% by weight        of active ingredient).    -   V. 80 parts by weight of a compound according to the invention        are mixed thoroughly with 3 parts by weight of sodium        diiso-butylnaphthalene-alpha-sulfonate, 10 parts by weight of        the sodium salt of a lignosulfonic acid from a sulfite waste        liquor and 7 parts by weight of pulverulent silica gel, and the        mixture is ground in a hammer mill (comprises 80% by weight of        active ingredient).    -   VI. 90 parts by weight of a compound according to the invention        are mixed with 10 parts by weight of N-methyl-α-pyrrolidone,        which gives a solution which is suitable for use in the form of        microdrops (comprises 90% by weight of active ingredient).    -   VII. 20 parts by weight of a compound according to the invention        are dissolved in a mixture composed of 40 parts by weight of        cyclohexanone, 30 parts by weight of isobutanol, 20 parts by        weight of the adduct of 7 mol of ethylene oxide and 1 mol of        isooctylphenol and 10 parts by weight of the adduct of 40 mol of        ethylene oxide and 1 mol of castor oil. Pouring the solution        into 100,000 parts by weight of water and finely distributing it        therein gives an aqueous dispersion which comprises 0.02% by        weight of the active ingredient.    -   VIII. 20 parts by weight of a compound according to the        invention are mixed thoroughly with 3 parts by weight of sodium        diisobutylnaphthalene-α-sulfonate, 17 parts by weight of the        sodium salt of a lignosulfonic acid from a sulfite waste liquor        and 60 parts by weight of pulverulent silica gel, and the        mixture is ground in a hammer mill. Finely distributing the        mixture in 20,000 parts by weight of water gives a spray mixture        which comprises 0.1% by weight of the active ingredient.

The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, e.g. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, scattering orpouring. The use forms depend entirely on the intended purposes; in anycase, this is intended to guarantee the finest possible distribution ofthe active ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances as suchor dissolved in an oil or solvent, can be homogenized in water by meansof wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can bevaried within substantial ranges. In general, they are from 0.0001 to10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even the activeingredient without additives.

Various types of oils, herbicides, fungicides, other pesticides, orbactericides may be added to the active ingredients, if appropriate alsoonly immediately prior to use (tank mix). These agents can be admixedwith the agents according to the invention in a weight ratio of 1:10 to10:1.

In the use form as fungicides, the compositions according to theinvention can also be present together with other active ingredients,e.g. with herbicides, insecticides, growth regulators, fungicides orelse with fertilizers. Mixing the compounds I or the compositionscomprising them in the use form as fungicides with other fungicidesfrequently results in a broader fungicidal spectrum of action.

The following list of fungicides, together with which the compoundsaccording to the invention can be used, is intended to illustrate thepossible combinations, but not to impose any limitation:

-   -   sulfur, dithiocarbamates and their derivatives, such as        iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate,        zinc ethylenebisdithiocarbamate, manganese        ethylenebis-dithiocarbamate, manganese zinc        ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide,        ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),        ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc        (N,N′-propylenebisdithiocarbamate),        N,N′-polypropylenebis(thiocarbamoyl)disulfide;    -   nitro derivatives, such as dinitro(1-methylheptyl)phenyl        crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,        2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl        5-nitro-isophthalate;    -   heterocyclic substances, such as 2-heptadecyl-2-imidazoline        acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine,        O,O-diethyl phthalimidophosphonothioate,        5-amino-1-[(bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,        2,3-dicyano-1,4-dithioanthraquinone,        2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl        1-(butylcarbamoyl)-2-benzimidazolecarbamate,        2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,        2-(4-thiazolyl)benzimidazole,        N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,        N-trichloromethylthiotetrahydrophthalimide,        N-trichloromethylthiophthalimide,        5-Chloro-2-cyano-4-p-tolyl-imidazole-1-sulfonic acid        dimethylamide,        N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfo-diamide,        5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,        2-thiocyanatomethylthiobenzothiazole,        1,4-dichloro-2,5-dimethoxybenzene,        4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,        pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt,        2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,        2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,        2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,        2-methylfuran-3-carboxanilide,        2,5-dimethylfuran-3-carboxanilide,        2-Chloro-N-(4′-chloro-biphenyl-2-yl)-nicotinamide,        2,4,5-trimethylfuran-3-carboxanilide,        N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,        N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,        2-methylbenzanilide, 2-iodobenzanilide,        N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,        piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,        1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane;        2,6-dimethyl-N-tridecylmorpholine or its salts,        2,6-dimethyl-N-cyclododecylmorpholine or its salts,        N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethyl-morpholine,        N-[3-(p-tert-butylphenyl)-2-methylpropyl]-piperidine,        1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,        1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,        N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolyl-urea,        1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,        1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,        (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole,        α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,        5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,        bis(p-chlorophenyl)-3-pyridinemethanol,        1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,        1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, strobilurines        such as azoxystrobin, kresoxim methyl,        methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]-acetamide, methyl        E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide,        picoxystrobin, pyraclostrobin, trifloxystrobin,        anilinopyrimidines such as        N-(4,6-dimethylpyrimidin-2-yl)aniline,        N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]-aniline,        N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline, phenylpyrroles        such as        4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,        cinnamamides such as        3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine,        3-(4-fluorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine,        and a variety of fungicides such as dodecylguanidine acetate,        3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,        hexachlorobenzene, methyl        N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,        DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl        ester,        N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone,        DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,        5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-di-oxo-1,3-oxazolidine,        3-[3,5-dichlorophenyl(5-methyl-5-methoxymethyl]-1,3-oxazolidine-2,4-dione,        3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,        N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,        2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,        3,5-Dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxo-propyl)-4-methyl-benzamide,        1-(3-Bromo-6-methoxy-2-methyl-phenyl)-1-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone,        1-[2-(2,4-dichloro-phenyl)pentyl]-1H-1,2,4-triazole,        2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,        N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,        1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

Synthesis Examples

With due modification of the starting compounds, the protocols shown inthe synthesis examples below were used for obtaining further compoundsI.

EXAMPLE 1 Preparation of diethyl (4,6-difluoro-2-methoxyphenyl)-malonate

Diethyl malonate (0.49 mol) was added to a mixture of sodium hydride(0.51 mol) and 1,4-dioxane (140 ml) at 60° C. within 2 hours. Themixture was stirred for 10 minutes at 60° C. and copper (I) bromide(0.05 mol) was added. After 15 minutes, a mixture of2-methoxy-4,6-difluorobromobenzene (0.25 mol) and 1,4-dioxane (10 ml)was added. The reaction mixture was stirred at about 100° C. for about15 hours. After cooling to about 15 to 20° C. 35 ml of 12N hydrochloricacid were added. The precipitate was filtered off. The filtrate wasextracted with diethyl ether. The organic phase was separated, dried andfiltered. The filtrate was evaporated to yield 44 g of the titlecompound.

EXAMPLE 2 Preparation of5,7-dihydroxy-6-(4,6-difluoro-2-methoxyphenyl)-[1,2,4]-triazolo-[1,5-α]pyrimidine

A mixture of 3-amino-1,2,4-triazole (14 g), 0.17 mmol of the malonatefrom Ex. 1 and tributylamine (50 ml) was stirred at 180° C. for sixhours. After cooling to 70° C. a solution of 21 g sodium hydroxide in200 ml water was added and the reaction mixture was stirred for 30minutes. The phases were separated and the aqueous phase was extractedwith diethyl ether. The aqueous phase was acidified with concentratedhydrochloric acid. The precipitate was collected by filtration and driedto yield 39 g of the title compound.

EXAMPLE 3 Preparation of5,7-dichloro-6-(4,6-difluoro-2-methoxyphenyl)-[1,2,4]-triazolo-[1,5-α]pyrimidine

A mixture of 30 g of the product from Ex. 2 and phosphorous oxychloride(50 ml) was refluxed for eight hours. Phosphorous oxychloride was partlydistilled off. The residue was poured into a mixture of dichloromethaneand water. The organic layer was separated, dried and filtered. Thefiltrate was concentrated to yield 29 g of the title compound of mp.122° C.

EXAMPLE 4 Preparation of5-chloro-6-(4,6-difluoro-2-methoxyphenyl)-7-(1,1,1-trifluoroprop-2-yl)amino-[1,2,4]-triazolo[1,5-α]pyrimidine[I-38]

A mixture of (1,1,1-trifluoroprop-2-yl)amine (7.5 mmol) and 1.5 mmol ofthe product from Ex. 3 was stirred for 16 hours at about 40° C. andsubsequently washed with 5% hydrocloric acid. The organic layer wasseparated, dried and filtered. The filtrate was evaporated and theresidue was chromatographed to yield 0.41 g of two separable rotamers ofthe title compound of mp. 181° C., and IR 1617, 1553, 1099 cm−¹, resp.

EXAMPLE 5 Preparation of5-cyano-6-(6-fluoro-2-methoxyphenyl)-7-diethylamino-[1,2,4]-triazolo[1,5-α]pyrimidine[I-42]

A mixture of 0.1 mol of compound [I-5] and (0.25 mol)tetraethyl-ammonium cyanide in 750 ml Dimethylformamide (DMF) wasstirred for 16 hours at 20 to 25° C. Water and methyl-tert.butylether(MTBE) were added to this mixture, the organic phase was separated,washed with water and dried. The solvent was evaporated under reducedpressure and the residue was purified through column chromatography toyield 5.93 g of the title compound of mp. 135° C.

EXAMPLE 6 Preparation of5-methoxy-6-(6-fluoro-2-methoxyphenyl)-7-diethylamino-[1,2,4]-triazolo[1,5α-]pyrimidine[I-43]

To a solution of 65 mmol of compound [I-5] in 400 ml of dry methanol asolution of sodium methanolate (30%, 71.5 mmol) was added at 20 to 25°C. This mixture was stirred for 16 hours at 20 to 25° C. Methanol wasevaporated and the residue was dissolved in dichloromethane. The organicphase was washed with water and dried. The solvent was evaporated underreduced pressure and the residue was purified through columnchromatography to yield 4.17 g of the title compound of mp. 114° C.

EXAMPLE 7 Preparation of5-methyl-6-(6-fluoro-2-methoxyphenyl)-7-diethylamino-[1,2,4]-triazolo[1,5-α]pyrimidine[I-44]

A mixture of 20 ml diethyl malonate and 0.27 g NaH of a 50% dispersionin mineral oil (5.65 mmol) in 50 ml acetonitrile was stirred at at 20 to25° C. for 2 hours. To this mixture 4.71 mmol of compound [I-5] wereadded. The reaction mixture was heated to 60° C. and stirred for 20hours. 50 ml of aqueous ammonium chloride were added and the mixture wasacidified with diluted HCl. The reaction mixture was extracted withMTBE. The combined organic phases were dried and concentrated. Theresidue was purified by column chromatography. The pure product obtainedwas diluted in concentrated HCl and heated to 80° C. for 24 hours. Thereaction mixture was cooled and adjusted to pH 5 by addition of aqueousNaOH. The reaction mixture was extracted with MTBE. The combined organicphases were dried, concentrated and purified by column chromatography toyield 0.72 g of the title compound.

¹H-NMR δ [ppm]: 8.33 (s); 7.42 (q); 6.85 (q); 3.80 (s); 3.35 (m); 3.25(m); 2.27 (s); 0.99 (t).

TABLE I I

No. R¹ R² L¹ L² X phys. data (m.p. [° C.]; IR [cm⁻¹]) I-1 CH₂C(CH₃)═CH₂CH₂CH₃ F H Cl 116 I-2 CH(CH₃)₂ H F H Cl 119 I-3 —(CH₂)₂CH(CH₃)(CH₂)₂— FH Cl 87 I-4 cyclopentyl H F H Cl 109 I-5 CH₂CH₃ CH₂CH₃ F H Cl 93 I-6CH₂CH₂CH₃ CH₂CH₂CH₃ F H Cl 109 I-7 CH(CH₃)₂ CH₃ F H Cl 119 I-8 (±)CH(CH₃)—CH₂CH₃ H F H Cl 98 I-9 (S) CH(CH₃)—CH₂CH₃ H F H Cl 112 I-10 (R)CH(CH₃)—CH₂CH₃ H F H Cl 112 I-l1 (±) CH(CH₃)—CH(CH₃)₂ H F H Cl 133 I-12(S) CH(CH₃)—CH(CH₃)₂ H F H Cl 136 I-13 (R) CH(CH₃)—CH(CH₃)₂ H F H Cl 136I-14 (±) CH(CH₃)—CH(CH₃)₃ H F H Cl 116 I-15 (S) CH(CH₃)—CH(CH₃)₃ H F HCl 176 I-16 (R) CH(CH₃)—CH(CH₃)₃ H F H Cl 176 I-17 (±) CH(CH₃)—CF₃ H F HCl 131 I-18 (S) CH(CH₃)—CF₃ H F H Cl 107 I-19 (R) CH(CH₃)—CF₃ H F H Cl108 I-20 CH₂CF₃ H F H Cl 182 I-21 H H F H Cl 247 I-22 CH₂C(CH₃)═CH₂CH₂CH₃ F F Cl 146 I-23 CH(CH₃)₂ H F F Cl 1614, 1574, 1097 I-24—(CH₂)₂CH(CH₃)(CH₂)₂— F F Cl 1595, 1532, 1096 I-25 cyclopentyl H F F Cl1612, 1574, 1095 I-26 CH₂CH₃ CH₂CH₃ F F Cl 112 I-27 CH₂CH₂CH₃ CH₂CH₂CH₃F F Cl 98 I-28 CH(CH₃)₂ CH₃ F F Cl 1595, 1526, 1093 I-29 (±)CH(CH₃)—CH₂CH₃ H F F Cl 1613, 1576, 1097 I-30 (S) CH(CH₃)—CH₂CH₃ H F FCl 1611, 1575, 1097 I-31 (R) CH(CH₃)—CH₂CH₃ H F F Cl 1611, 1576, 1098I-32 (±) CH(CH₃)—CH(CH₃)₂ H F F Cl A) 1612, 1575, 1098; B) 1611, 1576,1097 I-33 (S) CH(CH₃)—CH(CH₃)₂ H F F Cl A) 1612, 1575, 1098; B) 1611,1575, 1097 I-34 (R) CH(CH₃)—CH(CH₃)₂ H F F Cl A) 1611, 1575, 1098; B)1611, 1576, 1097 I-35 (±) CH(CH₃)—CH(CH₃)₃ H F F Cl A) mp. 126; B) 1612,1575, 1097 I-36 (S) CH(CH₃)—CH(CH₃)₃ H F F Cl A) mp. 145; B) 1610, 1583,1099 I-37 (R) CH(CH₃)—CH(CH₃)₃ H F F Cl A) mp. 144; B) 1610, 1583, 1099I-38 (±) CH(CH₃)—CF₃ H F F Cl cf. Example 4 I-39 (S) CH(CH₃)—CF₃ H F FCl A) mp. 150; B) 1610, 1579, 1097 I-40 (R) CH(CH₃)—CF₃ H F F Cl A) mp.150; B) 1617, 1554, 1099 I-41 CH₂CF₃ H F F Cl 253 I-42 CH₂CH₃ CH₂CH₃ F HCN 135 I-43 CH₂CH₃ CH₂CH₃ F H OCH₃ 114 I-44 CH₂CH₃ CH₂CH₃ F H CH₃ cf.Example 7 In some cases of chiral groups R¹ and due to the hinderedrotation of the phenyl group two diastereomers A) and B) exist which maydiffer in their physical properties.

Examples of the action against harmful fungi

The fungicidal action of the compounds of the formula I was demonstratedby the following experiments:

The active compounds, separately or together, were formulated as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying anddispersant action based on ethoxylated alkylphenols) and 10% by weightof Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) anddiluted with water to the desired concentration.

Use Example 1—Fungicidal control of leaf spot on beets (Cercosporabeticola)

Young sugar beet seedlings of the cultivar “ACH-31” were grown in potsto the 2 to 4 leaf stage. These plants were sprayed to runoff with anaqueous suspension, containing the concentration of active ingredientmentioned in the table below, prepared from a stock solution containing5% of the active ingredient, 94% cyclohexanone and 1% emulsifier (Tween20). After the plants had dried (3–5 h), they were inoculated with aspore suspension of Cercospora beticola in an aqueous solution of 0.5%gelatine. Then the trial plants were immediately transferred to a humidchamber with 18–23° C. and a relative humidity close to 100% and keptthere for 5 days. For a period of further 10–14 days a cultivation in agreenhouse followed at 21–23° C. and a relative humidity about 95%. Thenthe extent of fungal attack on the leaves was visually assessed as %diseased leaf area.

In this test, the plants which had been treated with 50 and 200 ppm,resp., of the mixture of both rotamers of Example 4 showed an infectionof not more than 7%, whereas the untreated plants were infected to 90%.

Use Example 2—Protective action on cucumber mildew

Leaves of pot grown cucumber seedlings of the “Chinesische Schlange”variety were sprayed to runoff with aqueous liquors made from a stocksolution consisting of 10% of active ingredient, 85% of cyclohexanone,and 5% of emulsifier. 20 hours after the sprays-on layer had dried, theplants were inoculated with a aqueous spore suspension of cucumbermildew (Sphaerotheca fuliginea). The plants were then placed for 7 daysin the greenhouse at 20 to 24° C. and a relative humidity of 60 to 80%.The extent of fungus spread was assessed as %-attack of the whole leafsurface.

In this trial, the plants which have been treated with 250 ppm ofcompounds I-24, I-32B, I-35A, and I-38B, resp., showed no infection,whereas the untreated plants were infected to 90%.

Use Example 3—Action on Botrytis cinerea on paprika leaves

Leaves of pot grown paprika seedlings at the four- to five-leave stageof the “Neusiedler Ideal Elite” variety were sprayed to runoff withaqueous liquors made from a stock solution consisting of 10% of activeingredient, 85% of cyclohexanone, and 5% of emulsifier. After 24 hoursthe plants were inoculated with a spore suspension of the fungusBotzytis cinerea (1.7×10⁶ spores per ml of a 2% strength biomaltsolution) and kept for 5 days at 20 to 24° C. and a high relativehumidity. Assessment was visual.

In this trial, the plants which have been treated with 250 ppm ofcompounds I-24, and I-29, resp., showed no infection, whereas theuntreated plants were infected to 85%.

Use Example 4—Action on Alternaria solani in tomatoes

Leaves of pot grown tomato seedlings of the “Groβe Fleischtomate St.Pierre” variety were sprayed with aqueous liquors made from a stocksolution consisting of 10% of active ingredient, 85% of cyclohexanone,and 5% of emulsifier. After 24 hours the leaves were infected with azoospore suspension of Alternaria solani (1.7×10⁶ spores per ml of a 2%strength biomalt solution). The plants were then placed in a watervapour-saturated chamber at 20 to 22° C. After 5 days the disease hadspread to such a great extent on the untreated plants that thefungicidal activity of the substances could be assessed.

In this trial, the plants which have been treated with 250 ppm ofcompounds I-32B, and I-35A, resp., showed an infection of not more than7%, whereas the untreated plants were infected to 90%.

1. Substituted 6-(2-methoxy-phenyl)-triazolopyrimidines of formula I

in which R¹ and R² independently denote hydrogen or C₁–C₁₀-alkyl,C₂–C₁₀-alkenyl, C₂–C₁₀-alkynyl, or C₄–C₁₀-alkadienyl, C₁–C₁₀-haloalkyl,C₂–C₁₀-haloalkenyl, C₃–C₁₀-cycloalkyl, phenyl, naphthyl, orC₃–C₁₀-cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl,containing one to four nitrogen atoms or one to three nitrogen atoms andone sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containingone to four nitrogen atoms or one to three nitrogen atoms and one sulfuror oxygen atom, or where R¹ and R² radicals may be unsubstituted orpartly or fully halogenated or may carry one to three groups R^(a),R^(a) is cyano, nitro, hydroxyl, C₁–C₆-alkyl, C₁–C₆-haloalkyl,C₃–C₆-cycloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkylthio,C₁–C₆-alkylamino, di-C₁–C₆-alkylamino, C₂–C₆-alkenyl, C₂–C₆-alkenyloxy,C₂–C₆-alkynyl, C₃–C₆-alkynyloxy and C₁–C₄-alkylenedioxy; or R¹ and R²together with the interjacent nitrogen atom represent a 5- or 6-memberedheterocyclic ring, containing one to four nitrogen atoms or one to threenitrogen atoms and one sulfur or oxygen atom, which may be substitutedby one to three R^(a) radicals; L¹, L² independently denote hydrogen orhalogen, provided that at least one from L¹ or L² is halogen; X ishalogen, cyano, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy orC₃–C₈-alkenyloxy.
 2. Compounds of formula I according to claim 1, inwhich R¹ is straight chained or branched C₁–C₆-alkyl, C₂–C₆-alkenyl,C₃–C₉-cycloalkyl, or C₁–C₁₀-haloalkyl, and R² is hydrogen orC₁–C₆-alkyl, or R¹ and R² together with the interjacent nitrogen atomrepresent a heterocyclic ring with 5 or 6 carbon atoms being optionallysubstituted with one or two C₁–C₆-alkyl groups.
 3. Compounds accordingto claim 1 in which R² is hydrogen.
 4. Compounds according to claim 1 inwhich X is halogen.
 5. A process for the preparation of compounds offormula I as defined in claim 4 which comprises reacting5-amino-1,2,4-triazole

with 2-phenyl-substituted malonic acid ester of formula II,

wherein L¹ and L² are as defined in formula I, and R denotesC₁–C₆-alkyl, under alkaline conditions, to yield compounds of formulaIII,

which are subsequently treated with a halogenating agent to give5,7-dihalogen-6-phenyl-triazolopyrimidines of formula IV

in which Y is halogen with an amine of formula V

in which R¹ and R² are as defined in formula I to produce compounds offormula I.
 6. A process for the preparation of compounds of formula Iaccording to claim 1 wherein X is cyano, C₁–C₁₀-alkoxy, orC₁–C₁₀-haloalkyl, which comprises reacting 5-halogen-triazolopyrimidineof formula I

with compounds of formula VI,M-X′  VI which are, dependent from the value of X′ to be introduced, ananorganic cyano salt, an alkoxylate, haloalkoxylate or analkenyloxylate, resp., wherein M is ammonium-, tetraalkylammonium-,alkalimetal- or earth metal cation, to produce compounds of formula I.7. Intermediates of formulae II, III, and IV as defined in claim
 5. 8. Acomposition suitable for controlling phytopathogenic fungi, comprising asolid or liquid carrier and a compound of the formula I as claimed inclaim
 1. 9. A method for controlling phytopathogenic fungi, whichcomprises treating the fungi or the materials, plants, the soil or theseed to be protected against fungal attack with an effective amount of acompound of the formula I as claimed in claim 1.